Chemicals



Patented June 4, 1946 i umreo sures PATENT OFFICE CHEMICALS Philip '1. Paul, Naugatuck, Conn., assignor to United States Rubber Company, New York, N. Y., a corporation or New Jersey No Drawing. Application January 13.1943, Serial N0. 472,272

1 Claim. (Cl. 260-573) 1 a w 2 This invention relates to a new class of chemlcal compounds called hydroxyl-alkyl substituted a N,N'-diaryl arylene diamines, and more partic- I ularly those of the general formula a a H A 5 111 l NCHICHrOOCCHI .NCHrCHzOOCCHr B I RI bx-R {6135 where R represents an aromatic group such as phenyl, naphthyl, etc., which may contain further substltuents; R is an arylene nucleus; and A represents a hydroxy alkyl group having at least twocarbon atoms in the chain.

This application is a continuation-in-part oi my application Serial No. 374,478, died January 15, 1941'.

The mono-hydroxyl alkyl substituted chemicals may be synthesized, for example, from (a) BBQ], 7 v dia -yum b fi st; reacting th am with l bICHiCHIOOCCHs ---r NCHIOHQOOCCHI -v kylene oxides, and then subsequently andsuci i p w cessively nitrosating, reducing. acetylating, congo v densinz with iodobenzene (or'a corresponding homolog or analog), and hydrolyzing to the mono-hydroxy alkylated material, Or (b) the mouoas well as the di-hydroxyl alkyl substi- N0 p tuted chemicals may be prepared in somewhat as less purified form by reacting a diaryl arylene diamine with an alkylene oxide (CnHInO), enabling the carbon chain of the alkylene group to be linked in the final compound to an original secondary amino nitrogen atombesides having 3 lQ Q the said carbon chain linked to a hydroxy group. a v The nitrogen atom and the hydroxy group are H joined to discrete carbon atoms. w w

The mechanic o! the (a) 'reaction is illus- V trated as follows in the preparation of mono a5 a N-(b-hydroxy ethyl) N,N'-diphenyl p-phenylene NHCWH' diamine. A symmetrical diaryl amine is heated with an alkyiene oxide to form an N-hydroxy alkyl diaryl amine. 1 This product is then nitroscated tat: afgnrll the para nitroso body (Cloez, 40

omp us 124, 8 8) which can be reduced to the amine by treatment with excess stannous a chloride. The acetyl derivative oi the amine may 11 5 be condensed with iodobenzene (Wieland, Ber. 41, 3493) and the resulting acetyl derivative hyv p drolyaed .with alcoholic potassium hydroxide. The scheme of the reaction i as follows:

COCHr COCK. H

In the event that a diaryl amine having both 5 para positions blocked is used as a starting materlal. the nitroeatlon will form an ortho nitroso substituted mine which will ultimately lead to an ortho phenylene diamine derivative.

least 2 and preferably 3 In the (b) reaction, a diaryl arylene diamine and an alkylene oxide is reacted by passing the alkylene oxide into a solution of a diaryl arylene diamine in an inert solvent, e. g., dioxane, benzene, etc., or into the molten diaryl arylene diamine. In general, it is necessary to effect this reaction at elevated temperatures of which a range of about 100 C. to about 200 C. is the preferred range. The reaction may be carried out by slowly passing the alkylene oxide into the heated diamine under atmospheric or under super atmospheric pressures. It is desirable that the diamine be stirred so as to continually expose fresh surface for hydroxyalkylation and to,

minimize the formation of N,N'-disubstituted material. The composition of the final product is controlled by the amount of the alkylene oxide reacted. To prepare a product which consists substantially of the mono-hydroxy alkylated material (as distinguished from the di-hydroxy alkylated material), between 1 and 2 mols of the oxide, more specifically 1%; mols of the alkylene oxide, are reacted with 1 mol of the diamine. To preparea di-hydroxy alkylated material, at or 4 mols of alkylene oxide per mol of the diamine are employed in the reaction. In general, to prepare the di-hydroxy alkylated derivatives, the preferred procedure is to use a large excess of oxide and to repeat the hydroxy alkylation, if necessary. It may be difiicult to isolate the mono-hydroxy alkylated body since, being an unsymmetrical material, it is low melting and usually a viscous liquid but, in general, a product consisting of a preponderant proportion, of mono-hydroxy alkylated material may be prepared by passing in an alkylene oxide to the diaryl arylene diamine until the unreacted diamine content drops to a low level, such as or less.

It is relatively easy to'separate unreacted oxide since this material is very volatile and the unreacted diamine can be substantially separated by extracting the crude product with an organic solvent such as alcohol .or benzene in which the diaryl arylene diamine is relatively insoluble. To isolate the mono-hydroxy alkylated derivative may be more difiicult, as referred to above, as this class of materials is characterized as low melting oils quite soluble in the usual organic solvents. The di-hydroxy alkylated material however can be isolated by a series of fractional crystallizations since these materials tend to be more crystallized than the mono-hydroxy alkylated bodies.

In the (b) reaction a catalyst usually is not necessary, especially in working with ethylene oxide, propylene oxide, or oxides of four-member rings. However, in the use of the 1,2-oxide of a highly branched carbon chain (isobutylene oxide) thereactivity is low and a catalyst accelerates the reaction. A number as catalysts of which the halogens, their acids and salts are particularly advantageous. Examples of such are bromine, iodine, hydrochloric acid, hydroiodic acid, ferrous chloride, lerrous iodide, aluminum chloride, sulfuric acid, and phosphoric acid.

Any residual acidity that may be associated with the products may be removed by neutralization with alkali an any known manner. Also, as is known in this art, suitable equipment is used to protect against any corrosion that may be-due to the acidic influence of the catalysts.

The following examples are given to further llustrate the invention:

of materials serve brown during C. at l-2 mm. mercury pressure.

Exammn 1.PREPARATION or N-(B-HYDROXY ETHYL) N,N'-DIPHENYL P-PHENATE DIAMINI:

Preparation of N-(b-hydroxy ethyDdiphenylamine A mixture of 33.8 gr. diphenylamine and 8.8 gr. ethylene oxide was heated 15 hours at 240-250 C. in a sealed tube. The tube was cooled, opened and the product cleaned up by a vacuum distillation. The product, a yellow oil, distilled 155-160" The yield is better than Acetylation of N-(b-hydroxy ethyl) diphenylamine Nitrosation of N-(b-acetoxy ethyl) diphenylamine A suspension of 79 gr. N-(b-acetoxy ethyl) diphenylamine in 250 cc. alcohol and 65 cc. concentrated hydrochloric acid was stirred and cooled to +5 C. With stirring a solution of 17.3 gr. sodium nitrite in 75 cc. water was added over a 30 minute period. The solution became dark the addition of the nitrite. It was allowed to stand in an ice bath for an additional 30 minutes.

Reduction of N-(b-acetomy ethyl) 4-m'troso diphenylamine To a solution of 169 gr. stannous chloride dihydratein cc. concentrated hydrochloric acid heated and stirred on a steam bath, the above alcoholic solution of the nitroso body was rapidly added. The color disappears almost immediately. The mixture after heating 15-30 minutes was cooled, aqueous sodium hydroxide. sufficient to neutralize and form soluble sodium stannitewas added, and the solution filtered through plugs of glass wool until essentially clear. The clarified solution was extracted with benzene, the benzene extract washed, dried, evaporated and vacuum distilled. Yield 50 grams of a yellow oil, B. R. 1'70-205 C. at 1 mm.

The acid reduction apparently caused some hydrolysis of the acetyl group as an odor of ethyl acetate was apparent at the end. However, this hydrolysis is not important since the acetyl group was immediately reintroduced in the next step.

standing, the acetyl derivative crystallized out. Yield 32.5 gr.

N-(b-acetorry ethyl) N'-acet l N,N-dlphenyl pphenylene diam ne A mixture of N-(b-acetoxy ethyl) 4-acetamino diphenylmine K200: (army) er 19.4 Copper powder gr.. 1/2 Methyl hexyl carbinol cc 100 was refluxed and stirred 25 hours. The mixture. 5

was cooled and the carbinol removed by steam distillation after which the non-volatile portion was extracted with benzene. The benzene extract was filtered, washed and evaporated. A1- cohol was added and the evaporation repeated.

N-(b-hydroxy ethyl) N,N'-diphenyl p-phenylene diamine To the residue from the alcohol evaporation,

gr. sodium hydroxide dissolved in 10 cc. water and 50 cc. alcohol was added and the solution refluxed 5 hours, cooled, diluted and extracted with benzene,

The benzene solution was washed, evaporated, and the residue fractionated.

Fraction Boiling range I 186-242" C. at 4 mm. H Mil-260 C. at 4 mm. In 270-280 C. at 4 mm.

Fraction II is N-(b-hydroxy ethyl) N, N'-diphenyl pphenylene diamine. EXAIPLE 2.-PREPARATION or N-(B-HYDROXY Errnn.) N,N-Drrmr. r-Prmn'rnnnn Drama rnou Ernnnm: Oxmr: AND Drrnam P-PHEN- YLIN'E Drumm In a 5 gallon steel autoclave equipped with a stirrer, 22 pounds, 14 ounces (1 mol) of technical diphenyl p-phenylene diamine was heated to 12 grams oi isobutylene oxide were autoclaved '15 hours at 200 C. The product on vacuum distilration gave two fractions: fraction lI-boiling range 225-250 C. at 3 mm. consisting of unreacted diphenyl p-phenylene diamine and traction H--boiling, range 260-265 C. at 3 mm. The

latter consists substantially of N,(b-hydroxy isob'utyl N,N'-diphenyl prphenylene diamine. It analyzed 8.8 percent nitrogen.

Exmru: 5

, boiling range 250-275 C. at 5 mm. was obtained.

175 C. Over an -8 hour period, 4 pounds, 10

ounces (1.24 mol) of ethylene oxide was passed .in. Heating and stirring were continued 1 hour and the contents discharged. The -product is a heavy viscous material consisting substantially oi N-(b-hydroxy ethyl) N,N'-diphenyl p-phenylene diamine.

EXAMPLE 3 Ethylene oxide (6 cc.) was condensed in a test tube in an acetone-dry ice bath and the tube closed so as to efiect a thin seal. -N,N'-diphenyl p-phenylene diamine (26 grams) was placed in a Carius tube along with a small piece of steel and the tube of ethylene oxide. After the Carius tube had been sealed it was shaken until the steel broke the test tube containing the ethylene oxide. The contents were then heated overnight at 175 C. and the product was purified by dissolving in acetone, filtering and removing the solvent by vacuum distillation. The product, a thick oil, analyzed 8.64 percent nitrogen and consisted of a mixture of N-(b-hydroxy ethyl) N,N'-diphenyl .p-phenylene diamine and N,N' dl-(b-hydroxy ethyl) N,N'-diphenyl p-phenylene diamine.

- Exnmn 4 Dlphenyl p-phenylene diamine (20 grams) and following Further examples of aliphatic oxides which may be reacted with any of the diamines are the n-Butylene oxide n-Amylene oxide Iso amylene oxide Trimethylene oxide Tetra methylene oxide Penta methylene oxide Other examples of N,N'-.diaryl arylene dlamines that could be used for reacting with any of the aliphatic oxides are the following:

Diphenyl meta-phenylene diamine Di-phenyl ortho-phenylene diamine Ditolyl p-phenylene diamine Di-p-anisyl p-phenylene diamine Di-alpha naphthyl p-phenylene diamine Di-beta naphthyl p-phenylene diamine Di-p-xenyl p-phenylene' diamine Di-p-chlorophenyl p-phenylene diamine Di-p-phenoxy diphenyl p-phenylene diamine Di(p-ethyl diphenyl) p-phenylene diamine Dlphenyl p-tolylene diamine Dlphenyl o-tolylene diamine 4-allyl 4'anilino diphenylamine 4-isopropeny1 4' anilino diphenylamine Dlphenyl 1-4 naphthalene diamine Di-p-hydroxy phenyl p-phenylene diamine The chemicals are useful as intermediates tor the preparation of chemicals, as insecticides, as

reservatives for rubber, gasolines, oils, soaps, un-

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